Compositions

ABSTRACT

The present invention provides a composition containing a particulate solid, an organic medium and/or water and a compound of Formula (1) and salts thereof: Formula (1) wherein R and R′ are independently H or  Cl-30 -optionally substituted hydrocarbyl; or R is H or  Cl-30 -optionally substituted hydrocarbyl and R′ is R″ C=O (an acyl group where R″ is hydrogen, alkyl or an optionally substituted alkyl or aryl or an optionally substituted aryl); Y is C 2-4 -alkyleneoxy; T is C 2-4  alkylene; A is the residue of a dibasic acid or anhydride thereof; Z is the residue of a polyamine and/or polyimine; W is the residue of an oxide, urea or dibasic acid or anhydride thereof, or mixtures thereof; x is from 2 to 90; and v represents the maximum available number of amino and/or imino groups in Z which does not carry the group RR′N-T-O-(Y)X-T-NH-A-.

CROSS REFERENCE TO RELATED APPLICATION

This application is filed pursuant to Provisional Application No.60/637,937 filed on Dec. 21, 2004.

FIELD OF INVENTION

The present invention relates to compositions comprising a particulatesolid, an organic medium and a dispersant and to their use in inks,millbases, plastics and paints.

BACKGROUND OF THE INVENTION

Many formulations such as inks, paints, mill-bases and plasticsmaterials require effective dispersants for uniformly distributing aparticulate solid in an organic medium. The organic medium may vary froma polar to non-polar organic medium. Consequently, dispersants aresought which can disperse a particulate solid in both a polar and anon-polar organic medium.

U.S. Pat. No. 4,224,212 discloses dispersants comprising a polyesterderived from a hydroxycarboxylic acid with at least 8 carbon atomsreacted with a poly(loweralkylene)imine. The dispersants are effectivein non-polar medium such as aliphatic solvents and plastics.

EP208041 discloses dispersants comprising a polyester derived fromε-caprolactone reacted with a poly(lower alkylene)imine. The dispersantsare effective in more polar medium such as ketones and esters.

U.S. Pat. No. 4,865,621 discloses motor fuel compositions comprising thereaction product of a dibasic acid anhydride, a polyoxyalkylenemonoamine and a hydrocarbyl polyamine having a number average molecularweight of up to 1343.

SUMMARY OF THE INVENTION

It has been found that certain dispersants show excellent ability todisperse a particulate solid in a range of organic media, particularlypolar organic media and including water. Thus, according to the presentinvention, there is provided a composition comprising a particulatesolid, an organic medium and/or water and a compound of Formula (1) andsalts thereof:

wherein

R and R′ are independently H or C₁₋₃₀-optionally substitutedhydrocarbyl; or R is H or C₁₋₃₀-optionally substituted hydrocarbyl andR′ is R″C=O (an acyl group);

R″ is hydrogen, alkyl or an optionally substituted alkyl or aryl or anoptionally substituted aryl;

Y is C₂₋₄-alkyleneoxy;

T is C₂₋₄ alkylene;

A is the residue of a dibasic acid or anhydride thereof;

Z is the residue of a polyamine and/or polyimine;

W is the residue of an oxide, urea or dibasic acid or anhydride thereof,or mixtures thereof;

x is from 2 to 90;

v represents the maximum available number of amino and/or imino groupsin Z which does not carry the group RR′N-T-O-(Y)_(x)-T-NH-A- (i.e., v isthe number of unsubstituted valences of Z) and 0-v means 0 to v.

Since Z is the residue of a polyamine and/or polyimine, there aretypically more than 2 groups RR′N-T-O-(Y)_(x)-T-NH-A- attached to Z andthese may be the same or different.

In the specific case wherein W is the residue of a dibasic acid, thereis provided a composition comprising a particulate solid, an organicmedium and a compound of formula (1a) and salts thereof:

wherein

R and R′ are independently H or C₁₋₃₀-optionally substitutedhydrocarbyl; or R can be H or C₁₋₃₀-optionally substituted hydrocarbyland R′ is R″C=O (an acyl group);

R″ is hydrogen, alkyl or an optionally substituted alkyl or aryl or anoptionally substituted aryl;

Y is C₂₋₄-alkyleneoxy;

T is C₂₋₄ alkylene;

A is the residue of a dibasic acid or anhydride thereof;

Z is the residue of a polyamine and/or polyimine;

x is from 2 to 90; and

A and A¹ are, independently, the residue of a dibasic acid or anhydridewhich may be the same or different; and

p is from 0 to 200.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a composition as described above.

In one embodiment, R is a hydrocarbyl including aryl, aralkyl, alkaryl,cycloalkyl or alkyl, which may be linear or branched. In one embodiment,R is alkyl, optionally a branched alkyl containing C₁₋₃₀, C₁₋₂₀, C₁₋₆ orC₁₋₄-alkyl. In one embodiment, R is a methyl.

When R is substituted hydrocarbyl, the substituent may be C₁₋₁₀-alkoxy,carbonyl, sulphonyl, carbamoyl, sulphamoyl, halogen, nitrile, ureido,hydroxyl, urethane or ester (i.e., —COO— or —OCO—). In one embodiment, Ris unsubstituted.

In one embodiment, R is aryl including naphthyl or phenyl. In oneembodiment, R is aralkyl including 2-phenylethyl or benzyl. In oneembodiment, R is alkaryl including octyl phenyl or nonyl phenyl. In oneembodiment, R is cycloalkyl including C₃₋₈-cycloalkyl such ascyclopropyl or cyclohexyl.

When Y is C₃₋₄-alkyleneoxy and the chain represented by (Y)_(x) containsethyleneoxy (—CH₂CH₂O—), the structure of (Y)_(x) may be random orblock. The chain represented by (Y)_(x) may contain only one type ofC₂₋₄-alkyleneoxy repeat unit or it may contain two or more differentC₂₋₄-alkyleneoxy repeat units. When the chain represented by (Y)_(x)contains two or more different C₂₋₄-alkyleneoxy repeat units, thestructure of (Y)_(x) may be random or block.

In one embodiment, Y is a C₃₋₄-alkyleneoxy group, —CH₂ CH₂CH₂CH₂O— or—CH₂CH(CH₃)CH₂O— or —CH₂CH(CH₃)O—. In another embodiment, Y is a—CH₂CH₂CH(CH₃)O— or —CH₂-CH(CH₂-CH₃)—O—.

When Y is C₃₋₄-alkyleneoxy, the chain represented by (Y)_(x) may containup to 95%, up to 75%, or up to 50% ethyleneoxy repeat units. Dispersantswherein (Y)_(x) contains more than 50% and especially more than 75%ethylene oxy repeat units are better suited to aqueous medium,optionally containing polar organic liquids.

When Y is C₃₋₄-alkyleneoxy and the chain represented by (Y)_(x) containsethyleneoxy (—CH₂CH₂O—), the structure of (Y)_(x) may be random orblock.

In one embodiment, the Y in Formula (1) is —CH₃CH(CH₃)O— and the chainrepresented by (Y)_(x) may contain up to 75% ethyleneoxy repeat units.

In one embodiment, T is a C₃₋₄-alkylene or —CH₂CH(CH₃)—. In oneembodiment, T is —CH₂CH(CH₃)— or —CH₂CH₂CH₂— when Y is —CH₂CH(CH₃)O—.

The group RR′N-T-O-(Y)_(x)-T-NH- in one embodiment is the residue of apolyalkyleneoxide diamine. Compounds of this type are commerciallyavailable as the Jeffamine™ D or ED-series of diamines from HuntsmanCorporation. Specific examples of Jeffamine™ diamines are D-230(3,0,230), D-400 (6,0,400), D-2000 (33,0,2000), D-4000 (68,0,4000),ED-600 (3.6,9,600), ED-900 (2.5,15.5,900) and ED2003 (6,39,2000). Thefigures in parentheses are approximate repeat units of propylene oxide,ethylene oxide and number-average molecular weight respectively.

When Z is the residue of a polyamine, it includes polyvinylamine orpolyallylamine. Polyallylamine and poly(N-alkyl)allylamines of differingmolecular weight are commercially available from Nitto Boseki.Polyvinylamine of differing molecular weight are available fromMitsubishi Kasei.

When Z is the residue of a polyimine, it includes poly(C₂₋₆-alkyleneimine) and especially polyethyleneimine (PEI). Thepolyimine may be linear or especially branched. Linear polyethyleneiminemay be prepared by the hydrolysis of poly(N-acyl) alkyleneimines asdescribed, for example, by Takeo Saegusa et al in Macromolecules, 1972,Vol 5, page 4470. Branched polyethyleneimines of differing molecularweight are commercially available from BASF and Nippon Shokubai.Polypropyleneimine dendrimers are commercially available from DSM FineChemicals and poly(amidoamine) dendrimers are available as “Starburst”dendrimers from Aldrich Chemical Company.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave as residuewhat is often termed “polyamine bottoms”. In general, alkylenepolyaminebottoms can be characterized as having less than two, usually less than1% (by weight) material boiling below about 200° C. A typical sample ofsuch ethylene polyamine bottoms obtained from the Dow Chemical Companyof Freeport, Texas designated “E-100” has a specific gravity at 15.6° C.of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40°C. of 121 centistokes. Gas chromatography analysis of such a samplecontains about 0.93% “Light Ends” (most probably DETA), 0.72% TETA,21.74% tetraethylene pentamine and 76.61% pentaethylenehexamine andhigher (by weight). These alkylenepolyamine bottoms include cycliccondensation products such as piperazine and higher analogs ofdiethylenetriamine or triethylenetetramine.

The number average molecular weight of the polyamine or polyimine in oneembodiment is from 300 to 650,000, 500 to 600,000, 600 to 200,000, 1,200to 100,000 or 1500 to 70,000. In the case of polyethyleneimine, thenumber-average molecular weight in one embodiment is not less than 1200,not less than 1800 or not less than 3,000.

The residue of dibasic acid represented by A and A¹ may be derived fromany dibasic acid of formula HOOC—B′—COOH or anhydride thereof wherein B′is a direct bond or a divalent organic moiety containing from 1 to 20carbon atoms. B′ may be aromatic, hetero aromatic, alicyclic oraliphatic which may be optionally substituted. When B′ is aliphaticcontaining two or more carbon atoms, it may be linear or branched,saturated or unsaturated. In one embodiment, B′ is unsubstituted. Inanother embodiment, B′ contains not greater than 12 carbon atoms and inanother embodiment not greater than 8 carbon atoms.

When B′ is aromatic, it includes phenylene, when B′ is alicyclic, itincludes cyclohexylene, and when B is aliphatic, it includes analkylene. In one embodiment, the dibasic acids are terephthalic,tetrahydrophthalic, methyl tetrahydrophthalic, hexahydrophthalic, methylhexahydrophthalic, trimellitic, C₁₋₂₀-alkenyl or alkyl succinic acids.In one embodiment, the dibasic acids are derived from maleic, malonic,succinic or phthalic acid. When the dibasic acid is derived from ananhydride suitable examples are derived from glutaric, succinic andphthalic anhydrides.

Mixtures of dibasic acids or anhydrides thereof may be used. Thus, A maybe the residue of one or more than one different dibasic acid oranhydride. In one embodiment, A is the residue of a single dibasic acidor anhydride. Similarly, A¹ may be the residue of one or more than onedifferent dibasic acid or anhydride. In one embodiment, A¹ is theresidue of a single dibasic acid or anhydride. In one embodiment, both Aand A¹ are the residue of the same dibasic acid or anhydride. In oneembodiment, A and/or A¹ is the residue of succinic anhydride.

When W is the residue of an oxide, any of the amino or imino groups in Zwhich do not carry the group RR′N-T-O-(Y)_(x)-T-NH-A- may be convertedto a N-oxide by reaction with oxygen (including air) or a peroxide suchas hydrogen peroxide or ammonium persulphate.

Similarly, when W is the residue of urea, the number of free aminoand/or imino groups in Z which are reacted with urea may vary over widelimits up to the maximum number of amino or imino groups which do notcarry the group RR′N-T-O-(Y)_(x)-T-NH-A-.

In one embodiment where W is the residue of a dibasic acid or anhydride,the majority of free amino or imino groups in Z which do not carry thegroup RR′N-T-O-(Y)_(x)-T-NH-A- are reacted with the dibasic acid oranhydride represented by A¹. In one embodiment, W is the residue of anoxide, the residue of urea or the residue of a dibasic acid oranhydride.

Thus, when p is other than zero in formula 1a, the majority ofamine/imine groups in Z which do not carry the groupRR′N-T-O-(Y)_(x)-T-NH-A- carry the residue -A¹-OH.

In one embodiment, the polyamine or polyimine represented by Z carries 2or more groups RR′N-T-O-(Y)_(x)-T-NH-A- which may be the same ordifferent. Dispersants of this type may be conveniently represented byFormula (2):

wherein

X-*-*-X represents the polyamine and/or polyimine;

Q is the chain RR′N-T-O-(Y)_(x)-T-NH-A-; and

q is from 2 to 2000.

In one embodiment, the polyamine or polyimine represented by Z carriestwo or more different polymer chains and is represented by formula 2a.

wherein

-   -   X-*-*-X and Q are as defined hereinbefore; and

Q¹ represents a polyester and/or polyamide chain of formulaR¹-G-(B)_(m−);

R¹ is hydrogen or C₁₋₅₀-optionally substituted hydrocarbyl;

G is a divalent bond or carbonyl;

B is the residue of one or more amino carboxylic acids, one or morehydroxy carboxylic acids, one or more lactones of hydroxycarboxylicacids, or mixtures thereof;

q and s are positive integers greater than zero;

m is a positive integer from 2 to 2000; and

q+s is from 2 to 2000.

In one embodiment, G is carbonyl and R¹-G- is the residue of aC₁₋₅₀-optionally substituted hydrocarbyl carboxylic acid and especiallya C₁₋₅₀-optionally substituted aliphatic acid where the aliphatic groupmay be saturated or unsaturated, linear or branched.

In one embodiment, R¹ contains not greater than 30 carbon atoms asdisclosed hereinbefore for R.

R¹—CO— may also be the residue of a linear or branched, saturated orunsaturated optionally substituted carboxylic acid such asmethoxy-acetic acid, propionic acid, butyric acid, hexanoic acid,octanoic acid, lauric acid, dodecanoic acid, stearic acid, 2-ethylbutyric acid, 2-ethyl hexanoic acid, 2-butyl octanoic acid, 2-hexyldecanoic acid, 2-octyl decanoic acid and 2-decyl tetra decanoic acid.Branched alkyl carboxylic acids of this type are also available underthe trade name Isocarb (ex Condea GmbH) and specific examples areIsocarb™ 12, 16, 20, 28, 32, 34T and 36.

When R¹ is substituted, the substituent may be one or more ether groupsor two or more ether groups. Thus, R¹—CO— may be the residue of anAkypo™ carboxylic acid (ex Kao Chem GmbH). Specific examples are AkypoLF1, Akypo LF2, Akypo RLM 25, Akypo RLM 45 CA, Akypo RO 20 VG and AkypoRO 50 VG.

The amino carboxylic acid from which B is obtainable includesamino-C₂₋₂₀-alk(en)ylene carboxylic acid or an amino C₁₋₂₀-alkylenecarboxylic acid. In one embodiment, the alk(en)ylene group contains notgreater than 12 carbon atoms. Specific examples are 11-amino undecanoicacid, 6-amino caproic acid, 4-amino butyric acid, β-alanine orsarcosine.

The hydroxy carboxylic acid from which B is derivable includes ahydroxy-C₂₋₂₀-alkenylene carboxylic acid or hydroxy-C₁₋₂₀ alkylenecarboxylic acid. Specific examples of suitable hydroxy carboxylic acidsare ricinoleic acid, 12-hydroxystearic acid, 6-hydroxy caproic acid,5-hydroxy valeric acid, 12-hydroxy dodecanoic acid, 5-hydroxy dodecanoicacid, 5-hydroxy decanoic acid, 4-hydroxy decanoic acid, 10-hydroxyundecanoic acid, lactic acid or glycolic acid.

B is also derivable from a lactone such as β-propiolactone, optionallyC₁₋₆-alkyl substituted ε-caprolactone and optionally C₁₋₆-alkylsubstituted δ-valerolactone. Specific examples are ε-caprolactone andthe 7-methyl-, 3-methyl-, 5-methyl-, 6-methyl-, 4-methyl-,5-tetra-butyl-, 4,4,6-trimethyl- and 4,6,6-trimethyl-ε-caprolactone andδ-valerolactone.

In one embodiment, the ratio of q to s is from 6:1 to 1:6.

As noted hereinbefore, the dispersant may be present in the form of asalt. Where the dispersant contains a carboxylic acid group, the saltmay be that of an alkali metal such as lithium, potassium or sodium.Alternatively, the salt may be formed with ammonia, an amine orquaternary ammonium cation. Examples of amines are methylamine,diethylamine, ethanolamine, diethanolamine, hexylamine,2-ethylhexylamine and octadecylamine. The quaternary ammonium cation maybe a quaternary ammonium cation or a benzalkonium cation. The quaternaryammonium cation may contain one or two alkyl groups containing from 6 to20 carbon atoms. Examples of quaternary ammonium cations are tetraethylammonium, N-octadecyl-N,N,N-trimethyl ammonium;N,N-didodecyl-N,N-dimethyl ammonium, N-benzyl-N,N,N-trimethyl ammoniumand N-benzyl-N-octadecyl-N,N-dimethyl ammonium cation.

In one embodiment, the dispersant containing a carboxylic acid group isin the form of a free acid.

The dispersant of formula 1 where v is zero may be in the form of a saltof a coloured acid. The coloured acid may be any anionic dyestuff suchas sulphonated or carboxylated copper or nickel phthalocyaninecontaining on average 0.5 to 3 sulphonic acid groups per molecule or adisazo dyestuff containing a sulphonic acid and/or carboxylic acidgroup.

When v is zero, some of the amine/imine groups in Z which do not carrythe group RR′N-T-O-(Y)_(x)-T-NH-A- may be converted into substitutedammonium groups by reaction with an acid or quaternising agent. Suitablereagents for this purpose include mineral and strong acids such ashydrochloric acid, acetic acid, sulphuric acid, alkyl sulphonic acids,alkyl hydrogen sulphates or aryl sulphonic acids. Quaternisating agentsinclude dimethyl sulphate, benzyl chloride, methyl halides such aschlorine, bromine and iodine, and propane (or butane) sultone.

The compound of Formula (1) may be made by any method known to the art.In one embodiment, the compound is prepared by the reaction of acompound of Formula (3) with a dibasic acid or anhydride thereof and apolyamine and/or a polyimine and optionally a second dibasic acid or ananhydride thereof.

RR′N-T-O-(Y)_(x)-T-NH₂   Formula 3

wherein R, R′, Y, T and x are as described hereinbefore.

In one embodiment, the compound of Formula (3) is reacted with the firstdibasic acid or anhydride at a temperature from 40 to 150° C. or from 60to 100° C. The reaction is typically performed in an inert atmosphere.The inert atmosphere may be provided by any inert gas of the PeriodicTable, although, nitrogen is commonly used.

The reaction with the polyamine and/or polyimine is carried out in oneembodiment at a temperature of from 100 to 200° C. Under suchconditions, the reaction results in a mixture of amide and salt formsrather than the salt form alone.

The reaction involving the optional second dibasic acid or anhydridethereof is typically carried out using similar conditions to thoseemployed using the first dibasic acid or anhydride thereof.

The reaction involving the first and the second dibasic acid oranhydride thereof may be carried out in the presence of an organicdiluent which is inert to the reactants. Similarly, the reaction betweenthe compound of formula 3 and the dibasic acid or anhydride thereof andthe polyamine and/or polyimine may also be carried out in the presenceof an organic diluent. In one embodiment, the organic diluent is asolvent for the reactants. The organic diluent may be aromatic oraliphatic including halogenated derivatives. Examples are toluene,chlorobenzene, heptane and petroleum ether distillates. Typically, thereaction is carried out in the absence of an organic diluent.

When W is the residue of an oxide, the number of amino and/or iminegroups in Z which do not carry the group RR′N-T-O-(Y)_(x)-T-NH-A- mayvary over wide limits. Such dispersants are easily prepared by reactingdispersants containing free amino and/or imino groups with an oxidizingcompound such as oxygen (or air) or a peroxide such as hydrogen peroxideor ammonium persulphate. Similarly, when W is the residue of urea suchdispersants may also be readily prepared by reacting any free aminoand/or imino groups in Z which do not carry the groupRR′N-T-O-(Y)_(x)-T-NH-A- with urea. The reaction in one embodiment iscarried out in an inert atmosphere at a temperature between 80° C. and140° C.

In one embodiment, R and R′ are hydrogen, thus forming a NH₂-moiety onthe compound of formula 1. The NH₂-moiety may further react with analkylation agent (e.g., methyl halides), an acylating agent (e.g.,acetic anhydride or acetyl chloride), esters, epoxides, (meth)acrylateor a lactone such as β-propiolactone, optionally C₁₋₆-alkyl substitutedε-caprolactone and optionally C₁₋₆-alkyl substituted δ-valerolactone.Specific examples of a suitable lactone include ε-caprolactone and the7-methyl-, 3-methyl-, 5-methyl-, 6-methyl-, 4-methyl-, 5-tetra- butyl-,4,4,6-trimethyl- and 4,6,6-trimethyl-ε-caprolactone and δvalerolactone.In one embodiment, the NH₂-moiety may be further reacted at atemperature in the range from 50° C. to 150° C.

In the specific case where W is the residue of a dibasic acid oranhydride thereof, the majority of amino and/or imino groups in Z whichdo not carry the group RR′N-T-O-(Y)_(x)-T-NH-A- are reacted with thedibasic acid or anhydride.

The particulate solid present in the composition may be any inorganic ororganic solid material which is substantially insoluble in the organicmedium. In one embodiment, the particulate solid is a pigment.

Examples of suitable solids are pigments for solvent inks; pigments,extenders and fillers for paints and plastics materials; disperse dyes;optical brightening agents and textile auxiliaries for solvent dyebaths,inks and other solvent application systems; solids for oil-based andinverse-emulsion drilling muds; dirt and solid particles in dry cleaningfluids; particulate ceramic materials; magnetic materials and magneticrecording media; fibers such as glass, steel, carbon and boron forcomposite materials, and biocides, agrochemicals and pharmaceuticalswhich are applied as dispersions in organic media.

In one embodiment, the solid is an organic pigment from any of therecognised classes of pigments described, for example, in the ThirdEdition of the Colour Index (1971) and subsequent revisions of, andsupplements thereto, under the chapter headed “Pigments”. Examples oforganic pigments are those from the azo, disazo, condensed azo,thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone,isodibenzanthrone, triphendioxazine, quinacridone and phthalocyanineseries, especially copper phthalocyanine and its nuclear halogenatedderivatives, and also lakes of acid, basic and mordant dyes. Carbonblack, although strictly inorganic, behaves more like an organic pigmentin its dispersing properties. In one embodiment, the organic pigmentsare phthalocyanines, especially copper phthalocyanines, monoazos,disazos, indanthrones, anthranthrones, quinacridones and carbon blacks.

Inorganic solids include: extenders and fillers such as talc, kaolin,silica, barytes and chalk; particulate ceramic materials such asalumina, silica, zirconia, titania, silicon nitride, boron nitride,silicon carbide, boron carbide, mixed silicon-aluminium nitrides andmetal titanates; particulate magnetic materials such as the magneticoxides of transition metals, especially iron and chromium, e.g.,gamma-Fe₂O₃, Fe₃O₄, and cobalt-doped iron oxides, calcium oxide,ferrites, especially barium ferrites; and metal particles, especiallymetallic iron, nickel, cobalt, copper and alloys thereof.

Other useful solid materials include agrochemicals such as thefungicides flutriafen, carbendazim, chlorothalonil and mancozeb.

The organic medium present in the composition of the invention in oneembodiment is a plastics material and in another embodiment an organicliquid. The organic liquid may be a non-polar or a polar organic liquid,although a polar organic liquid is typically used. By the term “polar”in relation to the organic liquid, it is meant that an organic liquid iscapable of forming moderate to strong bonds as described in the articleentitled “A Three Dimensional Approach to Solubility” by Crowley et alin Journal of Paint Technology, Vol. 38, 1966, at page 269. Such organicliquids generally have a hydrogen bonding number of 5 or more as definedin the abovementioned article.

Examples of suitable polar organic liquids are amines, ethers,especially lower alkyl ethers, organic acids, esters, ketones, glycols,alcohols and amides. Numerous specific examples of such moderatelystrongly hydrogen bonding liquids are given in the book entitled“Compatibility and Solubility” by Ibert Mellan (published in 1968 byNoyes Development Corporation) in Table 2.14 on pages 39-40 and theseliquids all fall within the scope of the term polar organic liquid asused herein.

In one embodiment, polar organic liquids are dialkyl ketones, alkylesters of alkane carboxylic acids and alkanols, especially such liquidscontaining up to, and including, a total of 6 carbon atoms. As examplesof the polar organic liquids include dialkyl and cycloalkyl ketones,such as acetone, methyl ethyl ketone, diethyl ketone, di-isopropylketone, methyl isobutyl ketone, di-isobutyl ketone, methyl isoamylketone, methyl n-amyl ketone and cyclohexanone; alkyl esters such asmethyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethylformate, methyl propionate, methoxy propylacetate and ethyl butyrate;glycols and glycol esters and ethers, such as ethylene glycol,2-ethoxyethanol, 3-methoxypropylpropanol, 3-ethoxypropylpropanol,2-butoxyethyl acetate, 3-methoxypropyl acetate, 3-ethoxypropyl acetateand 2-ethoxyethyl acetate; alkanols such as methanol, ethanol,n-propanol, isopropanol, n-butanol and isobutanol and dialkyl and cyclicethers such as diethyl ether and tetrahydrofuran. In one embodiment,solvents are alkanols, alkane carboxylic acids and esters of alkanecarboxlic acids.

Examples of organic liquids, which may be used as polar organic liquidsare film-forming resins such as are suitable for the preparation ofinks, paints and chips for use in various applications such as paintsand inks. Examples of such resins include polyamides, such as Versamid™and Wolfamid™, and cellulose ethers, such as ethyl cellulose and ethylhydroxyethyl cellulose, nitrocellulose and cellulose acetate butyrateresins, including mixtures thereof. Examples of paint resins includeshort oil alkyd/melamine-formaldehyde, polyester/melamine-formaldehyde,thermosetting acrylic/melamine-formaldehyde, long oil alkyd, polyetherpolyols and multi-media resins such as acrylic and urea/aldehyde.

The organic liquid may be a polyol, that is to say, an organic liquidwith two or more hydroxy groups. In one embodiment, polyols includealpha-omega diols or alpha-omega diol ethoxylates.

In one embodiment, non-polar organic liquids are compounds containingaliphatic groups, aromatic groups or mixtures thereof. The non-polarorganic liquids include non-halogenated aromatic hydrocarbons (e.g.,toluene and xylene), halogenated aromatic hydrocarbons (e.g.,chlorobenzene, dichlorobenzene, chlorotoluene), non-halogenatedaliphatic hydrocarbons (e.g., linear and branched aliphatic hydrocarbonscontaining six or more carbon atoms both fully and partially saturated),halogenated aliphatic hydrocarbons (e.g., dichloromethane, carbontetrachloride, chloroform, trichloroethane ) and natural non-polarorganics (e.g., vegetable oil, sunflower oil, linseed oil, terpenes andglycerides).

In one embodiment, the organic liquid comprises at least 0.1% by weight,or 1% by weight or more of a polar organic liquid based on the totalorganic liquid.

The organic liquid optionally further comprises water. In oneembodiment, the organic liquid is free of water.

When the organic liquid contains water, the amount of water present inone embodiment is not greater than 70%, is not greater than 50% or notgreater than 40% by weight based on the amount of organic liquid.

The plastics material may be a thermoset resin or a thermoplastic resin.The thermosetting resins useful in this invention include resins whichundergo a chemical reaction when heated, catalysed, or subject to UVradiation and become relatively infusible. Typical reactions inthermosetting resins include oxidation or unsaturated double bonds,reactions involving epoxy/amine, epoxy/carbonyl, epoxy/hydroxyl,polyisocyanate/hydroxy, amino resin/hydroxy moieties, free radicalreactions or polyacrylate, cationic polymerization or epoxy resins andvinyl ether, condensation or silanol, etc.

Polymers with hydroxy functionality (frequently polyols) are widely usedin thermosetting system to crosslink with amino resins orpolyisocyanates. The polyols include acrylic polyols, alkyd polyols,polyester polyols, polyether polyols and polyurethane polyols. Typicalamino resins include melamine formaldehyde resins, benzoguanamineformaldehyde resins, urea formaldehyde resins and glycolurilformaldehyde resins. Polyisocyanates are resins with two or moreisocyanate groups, including both monomeric aliphatic diisocyanates,monomeric aromatic diisocyanates and their polymers. Typical aliphaticdiisocyanates include hexamethylene diisocyanate, isophoronediisocyanate and hydrogenated diphenylmethane diisocyanate. Typicalaromatic isocyanates include toluene diisocyanates and biphenylmethanediisocyanates.

In one embodiment, thermoplastic resins include polyolefins, polyesters,polyamides, polycarbonates, polyurethanes, polystyrenics,poly(meth)acrylates, celluloses and cellulose derivatives. Saidcompositions may be prepared in a number of ways but melt mixing and drysolid blending are typical methods.

If desired, the compositions may contain other ingredients, for example,resins (where these do not already constitute the organic medium),binders, fluidizing agents anti-sedimentation agents, plasticizers,surfactants, anti-foamers, rheology modifiers, leveling agents, glossmodifiers and preservatives.

The compositions typically contain from 1 to 95% by weight of theparticulate solid, the precise quantity depending on the nature of thesolid and the quantity depending on the nature of the solid and therelative densities of the solid and the polar organic liquid. Forexample, a composition in which the solid is an organic material, suchas an organic pigment, in one embodiment contains from 15 to 60% byweight of the solid whereas a composition in which the solid is aninorganic material, such as an inorganic pigment, filler or extender, inone embodiment contains from 40 to 90% by weight of the solid based onthe total weight of composition.

The composition may be prepared by any of the conventional methods knownfor preparing dispersions. Thus, the solid, the organic medium and thedispersant may be mixed in any order, the mixture then being subjectedto a mechanical treatment to reduce the particles of the solid to anappropriate size, for example by ball milling, bead milling, gravelmilling or plastic milling until the dispersion is formed.Alternatively, the solid may be treated to reduce its particle sizeindependently or in admixture with either the organic medium or thedispersant, the other ingredient or ingredients then being added and themixture being agitated to provide the composition.

The composition of the present invention is particularly suited toliquid dispersions. In one embodiment, the dispersion compositioncomprises:

-   -   a) from 0.5 to 30 parts of a particulate solid;    -   b) from 0.5 to 30 parts of a compound of Formula (1); and    -   c) from 40 to 99 parts of an organic liquid;        wherein all parts are by weight and the amounts (a)+(b)+(c)=100.

In one embodiment, component a) comprises from 0.5 to 30 parts of apigment and such dispersions are useful as liquid inks, paints andmill-bases.

If a composition is required comprising a particulate solid and adispersant of Formula (1) in dry form, the organic liquid is typicallyvolatile so that it may be readily removed from the particulate solid bya simple separation means such as evaporation. In one embodiment, thecomposition comprises the organic liquid.

If the dry composition consists essentially of the dispersant of Formula(1) and the particulate solid, it typically contains at least 0.2%, atleast 0.5% or at least 1.0% dispersant of Formula (1) based on weight ofthe particulate solid. In one embodiment, the dry composition containsnot greater than 100%, not greater than 50%, not greater than 20% or notgreater than 10% by weight of dispersant of Formula (1) based on theweight of the particulate solid.

As disclosed hereinbefore, the compositions of the invention aresuitable for preparing mill-bases wherein the particulate solid ismilled in an organic liquid in the presence of a compound for Formula(1) and salts thereof.

Thus, according to a still further aspect of the invention there isprovided a mill-base comprising a particulate solid, an organic liquidand a compound of Formula (1) and salts thereof.

Typically, the mill-base contains from 20 to 70% by weight particulatesolid based on the total weight of the mill-base. In one embodiment, theparticulate solid is not less than 10 or not less than 20% by weight ofthe mill-base. Such mill-bases may optionally contain a binder addedeither before or after milling.

The binder is a polymeric material capable of binding the composition onvolatilisation of the organic liquid.

Binders are polymeric materials including natural and syntheticmaterials. In one embodiment, binders include poly(meth)acrylates,polystyrenics, polyesters, polyurethanes, alkyds, polysaccharides suchas cellulose, and natural proteins such as casein. In one embodiment,the binder is present in the composition at more than 100% based on theamount of particulate solid, more than 200%, more than 300% or more than400%.

The amount of optional binder in the mill-base can vary over wide limitsbut is typically not less than 10%, and often not less than 20% byweight of the continuous/liquid phase of the mill-base. In oneembodiment, the amount of binder is not greater than 50% or not greaterthan 40% by weight of the continuous/liquid phase of the mill-base.

The amount of dispersant in the mill-base is dependent on the amount ofparticulate solid but is typically from 0.5 to 5% by weight of themill-base.

Dispersions and mill-bases made from the composition of the inventionare particularly suitable for use in coatings and paints, especiallyhigh solids paints; inks, especially flexographic, gravure and screeninks; non-aqueous ceramic processes, especially tape-coating,doctor-blade, extrusion and injection molding type processes;composites, cosmetics, adhesives and plastics materials.

Thus, according to a further aspect of the present invention, there isprovided a paint or ink comprising a particulate solid, an organicliquid, a binder and a compound of Formula (1) and salts thereof.

As noted hereinbefore, many of the dispersants of Formula (1) are novel.

Thus, according to a further aspect of the invention, there is provideda compound of Formula (4) and salts thereof:

wherein R, R′, Y, T, A, Z, A¹, x, (Y)_(x) and the salts are as definedhereinbefore and r is from 1 to 200.

In one embodiment, the compound of Formula (4) and salts thereof isprovided wherein R, R′, T, A, Z, A¹, x, the salts and r are as definedhereinbefore, Y is C₃₋₄-alkyleneoxy and the chain represented by (Y)_(x)may contain up to 75% by number of ethyleneoxy repeat units.

According to a still further aspect of the invention, there is provideda compound of Formula (1) and salts thereof wherein Z is a polyamineand/or polyimine having a number average molecular weight of not lessthan 1200 and where v is zero.

In one embodiment, the compound of Formula (1) and salts thereof isprovided wherein Y is C₃₋₄-alkyleneoxy, the chain represented by (Y)_(x)may contain up to 75% by number of ethyleneoxy repeat units and Z is apolyamine and/or polyimine having a number average molecular weight ofnot less than 1200.

According to a still further aspect of the invention, there is provideda compound of formula 5:

wherein R, R′, Y, T, A, Z, x and v are as defined hereinbefore and W isthe residue of an oxide or urea.

In one embodiment, the compound is obtainable/obtained from the reactionof a diamine, a polyamine and/or polyimine and a dibasic acid oranhydride thereof. Consequently, a person skilled in the art willappreciate that a compound may include a mixture of products fromformulae 1, 1a, 4 and 5. Furthermore, compounds may include moietieswith one or more unreacted amines, 1 or more carboxylic acid oranhydride functional groups or 1 or more amide functional groups. Theinvention further includes any of the compounds obtainable from thereaction of a diamine, a polyamine and/or polyimine and a dibasic acidor anhydride thereof as described herein.

The invention is further illustrated by the following examples whereinall references to amounts are in parts by weight unless indicated to thecontrary.

EXAMPLES Example 1 1:1 Jeffamine D2000:Succinic Anhydride

Jeffamine D2000 (400 g 200 mmols, ex Huntsman) and succinic anhydride(20 g 200 mmols, ex Aldrich) is stirred at 80° C. for 18 hours under anitrogen atmosphere to give a viscous yellow liquid (418 g), IR showedno presence of an anhydride group and the presence of a carbonyl amide(1659 cm⁻¹). Acid value of the mixture is measured as 26.3 mg KOH/g andbase equivalent as 2026. This is Intermediate 1.

Polyethyleneimine SP030 (3.1 g 1 mmol, ex Nippon Shokubai MW 3000) isadded to stirred intermediate 1 (40 g 19 mmols) at 80° C. under anitrogen atmosphere. After 15 minutes, the whole mixture is stirred at120° C. for 6 hours under a nitrogen atmosphere to give a viscous ambergum (41 g). The acid value of the mixture is measured as 16 mg KOH/g.This is Dispersant 1.

The reaction above is repeated using various MW polyethyleneimines.

Example 2 13:1 (1:1:1 Jeffamine D2000:Succinic Anhydride:AceticAnhydride): Polyethyleneimine SP200

Acetic anhydride (2.13 g 20.9 mmols, ex Fisher) is added to stirredIntermediate 1 (40 g 19 mmols) at 80° C. under a nitrogen atmosphere.The whole mixture is stirred at 80° C. for 6 hours under a nitrogenatmosphere to give a pale yellow liquid. The acid value of the mixtureis measured as 26.6 mg KOH/g and there is no base equivalent valueindicating complete reaction of the amine groups. IR showed no presenceof an anhydride group and the presence of a carbonyl amide (1649 cm⁻¹).This is Intermediate 2.

Polyethyleneimine SP200 (3.1 g 0.03 mmols, ex Nippon Shokubai MW 10000)is added to stirred intermediate 2 (40 g 19 mmols) at 80° C. under anitrogen atmosphere. After 15 minutes, the whole mixture is stirred at120° C. for 6 hours under a nitrogen atmosphere to give a viscous ambergum (42 g). The acid value of the mixture is measured as 15.8 mg KOH/g.This is Dispersant 2.

Example 3 to 36

Dispersants 3 to 36 are prepared in a similar process to eitherDispersant 1 and/or 2. The chemicals used to prepare Dispersants 3 to 36are shown in Table 1(a) to Table 1(c). Dispersants 31 to 34 are preparedby further reactions as follows:

Dispersant 2 (16 g) is gently stirred in toluene (16 g) at 80° C. undera nitrogen atmosphere and succinic anhydride (0.87 g, ex Aldrich) isadded. The mixture is stirred at 80° C. for 2 hours or until noanhydride is detectable by IR. An orange solution (32 g) is obtained.This is Dispersant 31.

Dispersant 12 (20 g) and urea (0.65 g ex Aldrich) are stirred togetherat 120° C. for 24 hours under a nitrogen atmosphere. A brown viscousliquid (20 g) is obtained. This is Dispersant 32.

Dispersant 11 (20 g) and 35 wt % of aqueous hydrogen peroxide solution(1.06 g ex Fisher) is stirred together at 80° C. under a nitrogenatmosphere until the peroxide has substantially reacted as confirmed bya negative result using starch iodide paper. A brown, viscous liquid (20g) is obtained. This is Dispersant 33.

Dispersant 21 (16 g) and dimethyl sulphate (DMS) (0.16 g ex Aldrich) arestirred together at 90° C. under a nitrogen atmosphere until the DMS hassubstantially reacted as confirmed by a negative result usingbromocresol green indicator. A pale yellow viscous liquid (16 g) isobtained. This is Dispersant 34.

TABLE 1(a) Disper- Acylating sant Jeffamine Anhydride Agent PEI Ratio 3D2000 Succinic None Epomin 13:1 SP006 4 D2000 Succinic None Epomin 13:1SP018 5 D2000 Glutaric Acetic Epomin 12:1 Anhydride SP050 6 D2000Succinic None TEPA 13:1 7 D2000 Succinic Acetic Epomin 13:1 AnhydrideSP006 8 D2000 Succinic Acetic Epomin 13:1 Anhydride SP012 9 D2000Succinic Acetic Epomin 13:1 Anhydride SP018 10 D2000 Succinic AceticEpomin 13:1 Anhydride SP30 11 D2000 Succinic Acetic Epomin 13:1Anhydride SP050 12 D2000 Succinic Acetic Epomin 13:1 Anhydride SP075 13D2000 Diglycolic Acetic Epomin 11:1 Anhydride SP200 14 D2000 SuccinicAcetic Epomin 13:1 Anhydride SP300

TABLE 1(b) Disper- Acylating sant Jeffamine Anhydride Agent PEI Ratio 15D2000 Succinic Acetic TEPA 13:1 Anhydride 16 D2000 Succinic AceticEpomin 7:1 Anhydride SP030 17 D2000 Succinic Acetic Epomin 7:1 AnhydrideSP075 18 D2000 Succinic Acetic Epomin 6:1 Anhydride SP200 19 D2000Succinic Acetic Epomin 5:1 Anhydride SP300 20 D2000 Succinic AceticEpomin 20:1 Anhydride SP012 21 D2000 Succinic Acetic Epomin 18:1Anhydride SP200 22 ED900 Succinic Acetic Epomin 6:1 Anhydride SP075 23ED2001 Succinic Acetic Epomin 6:1 Anhydride SP075 24 Poly THF SuccinicAcetic Epomin 6:1 bisamine Anhydride SP075 25 ED2001 Succinic AceticEpomin 10.5:1 Anhydride SP300 26 ED2001 Succinic Acetic Epomin 16:1Anhydride SP030 27 D2000 Diglycolic Acetic Epomin 6:1 Anhydride SP075

TABLE 1(c) Disper- Acylating sant Jeffamine Anhydride Agent PEI Ratio 28D2000 Succinic None Epomin SP200 8:1 29 D2000 Succinic AceticPolyallylamine 10:1 Anhydride MW 17,000 30 D2000 Succinic AceticPolyallylamine 18:1 Anhydride MW 17,000 31 D2000 Succinic Acetic EpominSP200 13:1 Anhydride 32 D2000 Succinic Acetic Epomin SP075 13:1Anhydride 33 D2000 Succinic Acetic Epomin SP050 13:1 Anhydride 34 D2000Succinic Acetic Epomin SP200 18:1 Anhydride 35 ED2001 Succinic AceticPolyallylamine 18:1 Anhydride MW 17,000 36 D2000 Succinic CaprolactoneEpomin SP200 13:1 Footnote to Table 1(a) to 1(c): PEI ispolyethyleneimine commercially available from Nippon Shokubai asEpomin ™.

Example 37

Jeffamine D2000 (400 g 200 mmols, ex Huntsman) and succinic anhydride(30 g 300 mmols, ex Aldrich) are stirred at 80° C. for 18 hours under anitrogen atmosphere. This is Intermediate 3.

Acetic anhydride (1.06 g 10.4 mmols, ex Fisher) is added to stirredintermediate 3 (40 g 19 mmols) at 80° C. under a nitrogen atmosphere.The whole mixture was stirred at 80° C. for 6 hours under a nitrogenatmosphere. This is Intermediate 4.

Polyethyleneimine SP075 (5.7 g 0.76 mmols, ex Nippon Shokubai MW 7500)is added to stirred intermediate 4 (40 g 19 mmols) at 80° C. under anitrogen atmosphere. After 15 minutes, the whole mixture is stirred at120° C. for 6 hours under a nitrogen atmosphere. This is Dispersant 37.

Preparation of Mill-Bases

A series of magenta mill-bases were prepared utilizing Dispersants 1 to40. The mill-bases were prepared by dissolving dispersant 1 or 2 (0.65g) in a solvent mixture of 7.55 g MPA:Butanol ratio of 4:1(MPA=methoxypropylacetate). Glass beads (3 mm, 17 parts) and MonoliteRubine 3B (ex Heubach 2.0 parts) were added and the mixture was shakenon a horizontal shaker for 16 hours. A comparative example is preparedin the absence of dispersant. The resulting dispersions were thenassessed for fluidity using an arbitrary scale of A to E (good to bad).The results obtained are shown in Table 2.

TABLE 2 Milling Grade in 4:1 Dispersant MPA:Butanol 1 B/C 2 B 3 D/E 4D/E 5 B 6 E 7 E 8 D/E 9 C 10 B 11 B 12 B 13 A/B 14 C 15 E 16 C/D 17 B 18B 19 C/D 20 E 21 B 22 B/C 23 B 24 C 25 B 26 B 27 B 28 A/B 29 A 30 A 31 A32 A 33 — 34 — 35 A/B 36 — Control 1 C Control 2 C Control 3 EFootnote to Table 2: Control 1 is polycaprolactone end-capped withlauric acid and reacted with polyethyleneimine as described in U.S. Pat.No. 4,645,611. Control 2 is Example 1 of U.S. Pat. No. 6,197,877; andControl 3 uses no dispersing agent.

Tables 2 show that dispersants of the present invention give goodfluidity with organic media of very different polarities.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention maybe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of” permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

1. A composition comprising a particulate solid, an organic mediumand/or water and a compound of Formula (1) and salts thereof:

wherein R and R′ are independently H or C₁₋₃₀-optionally substitutedhydrocarbyl; or R is H or C₁₋₃₀-optionally substituted hydrocarbyl andR′ is R″C=O (an acyl group); R″ is hydrogen, alkyl or an optionallysubstituted alkyl or aryl or an optionally substituted aryl; Y isC₂₋₄-alkyleneoxy; T is C₂₋₄ alkylene; A is the residue of a dibasic acidor anhydride thereof; Z is the residue of a polyamine and/or polyimine;W is the residue of an oxide, urea or dibasic acid or anhydride thereof,or mixtures thereof; x is from 2 to 90; and v represents the maximumavailable number of amino and/or imino groups in Z which does not carrythe group RR′N-T-O-(Y)_(x)-T-NH-A-, and 0-v means to 0 to v.
 2. Thecomposition as claimed in claim 1 comprising a particulate solid, anorganic medium and a compound of Formula (1a) and salts thereof:

wherein R and R′ are independently H or C₁₋₃₀-optionally substitutedhydrocarbyl; or R is H or C₁₋₃₀-optionally substituted hydrocarbyl andR′ is R″C=O (an acyl group); R″ is hydrogen, alkyl or an optionallysubstituted alkyl or aryl or an optionally substituted aryl; Y isC₂₋₄-alkyleneoxy; T is C₂₋₄ alkylene; A is the residue of a dibasic acidor anhydride thereof; Z is the residue of a polyamine and/or polyimine;x is from 2 to 90; and A and A¹ are, independently, the residue of adibasic acid or anhydride which may be the same or different; and p isfrom 0to200.
 3. The composition as claimed claim 1 wherein Y isC₃₋₄-alkyleneoxy and the chain represented by (Y)_(x) may contain up to75% by number of ethyleneoxy repeat units.
 4. The composition as claimedin claim 1 wherein A is the residue independently derived from the groupconsisting of maleic acid, malonic acid, succinic and phthalic acid,glutaric anhydride, succinic anhydride and phthalic anhydride.
 5. Thecomposition as claimed in claim 2 wherein A′ is the residueindependently derived from the group consisting of maleic acid, malonicacid, succinic and phthalic acid, glutaric anhydride, succinic anhydrideand phthalic anhydride.
 6. The composition as claimed in claim 1 whereinthe group represented by Z is polyethyleneimine.
 7. The composition asclaimed in claim 1 wherein the organic medium is an organic liquid or aplastics material.
 8. The composition as claimed in claim 1 wherein theorganic liquid comprises at least 0.1% by weight of a polar organicliquid based on the total organic liquid.
 9. The composition as claimedin claim 1 wherein the particulate solid is a pigment.